Copper-Catalyzed Cross-Coupling of Alkyl and Phosphorus Radicals for C(sp3)-P Bond Formation.

A CuI-catalyzed cross-coupling of alkyl- and phosphorus-centered radicals for C(sp3)-P bond formation is introduced. Diacyl peroxides, generated in situ from aliphatic acids and H2O2, serve as a source for alkyl radicals and also an initiator for the generation of phosphorus radicals from H-P(O) compounds.

Copper-Catalyzed Vicinal Cyano-, Thiocyano-, and Chlorophosphorylation of Alkynes: A Phosphinoyl Radical-Initiated Approach for Difunctionalized Alkenes.

A copper-catalyzed difunctional cyano-, thiocyano-, and chlorophosphorylation reaction of alkynes with P(O)-H compounds and coupling partners (TBACN, TMSNCS, TMSCl) is described. The reaction introduces versatile groups (-P(O)R2 and -CN, -SCN, or -Cl) to form tri- and tetrasubstituted alkenyl phosphine oxides/phosphonates regio- and stereoselectively.

Copper-Catalyzed Oxidative sp3-Carbon Radical Cross-Coupling with Trialkylphosphites Leading to α-Phosphonyl 1,3-Dicarbonyl Compounds.

A copper-catalyzed radical Csp3-H/P(OR)3 cross-coupling reaction for the formation of Csp3-P bonds is described. A range of 1,3-dicarbonyl compounds and trialkylphosphites were coupled in this fashion to give the corresponding products in moderate to good yields. This protocol provides direct access to α-phosphonyl 1,3-dicarbonyl compounds.

Visible Light-Mediated Photocatalytic Metal-Free Cross-Coupling Reaction of Alkenyl Carboxylic Acids with Diarylphosphine Oxides Leading to ß-Ketophosphine Oxides.

A new visible light-mediated photocatalytic decarboxylative oxyphosphorylation of cinnamic acids with diarylphosphine oxides is described. This reaction is performed under mild conditions to afford the corresponding ß-ketophosphine oxides.

Phosphinoyl Radical-Initiated 1,2-Bifunctional Thiocyanodiphenylphosphinoylation of Alkenes.

1,2-Bifuctional thiocyanodiphenylphosphinoylation of alkenes is established through the phosphinoyl radical addition followed by Cu-catalyzed thiocyanation. This one-pot reaction is applicable to a range of aromatic, aliphatic, and cyclic alkenes to afford thiocyanodiphenylphosphinoylated compounds in satisfactory yields.